Dehydrofluorination of hydrocarbons



Aprll 1953 cs. T. LEATHERMAN DEl-IYDROFLUORINATION OF HYDROCARBONS Filed July 29, 1949 llll 1 A uolvavdas mOkU um IN VEV TOR.

N A M R E m A E L T G mmJOOU A TTORNEYS Patented Apr. 28, 1953 DEHYDROFLUORINATION OF HYDROCARBONS Gerald T. Leatherman, Bartlesville, kla., assignor to Phillips Petroleum Company, a corporation of Delaware Application July 29, 1949, Serial No. 107,585

8 Claims.

This invention relates to the treatment of organic materials to remove therefrom organic fluorine-containing compounds. In one of its more specific aspects, it relates to the removal from hydrocarbon materials of fluorine-containing compounds. In another of its more specific aspects, it relates to the removal of at least a major portion of organically bound fluorine from hydrocarbon materials containing organically bound flourine in an amount not greater than 1 per cent by weight and often in an amount not greater than between 0.1 and 0.05 per cent by weight.

In the manufacture of hydrocarbons by processes in which fluorine-containing catalysts are used, small proportions of organic fluorine-containing by-products are formed. These processes may involve reactions such as polymerization, a lrylation, and isomerization of relatively low boiling hydrocarbons to produce motor fuel hydrocarbons in the presence of catalysts comprising one or more of such fluorine compounds as hydrofluoric acid, boron trifluoride, and the like. Although the exact nature or composition of the organic fluorine-containing by-products which may be formed has not been definitely established, they are believed to be predominantly alkyl and/or aryl fluorides. Such fluorides are not completely removed by washing the hydrocarbons with alkali solutions. decompose at elevated temperatures, such as those employed in fractional distillation of the hydrocarbons, thereby forming hydrofluoric acid, which is corrosive, especially in the presence of moisture. In gases, they may thus cause corrosion of handling equipment; in liquid motorfuel hydrocarbons, they are undesirable for reasons that are obvious.

Organic fluorine compounds have conventionally been removed from hydrocarbon material They tend to containing them by contacting such hydrocarbon though the exact mechanism involved is not fully known at present, and the fluorine remains bound with, or associated with, the contact material. The hydrocarbon material being treated may be in either the liquid or the vapor phase. Removal of the organic fluorine compounds in this manner has proved to be quite expensive because of the loss of considerable amounts of hydrogen fluoride. When dehydrated bauxite is used as the contact material, considerable expense has also been encountered because of the cost of the bauxite which is ordinarily discarded after it has adsorbed its maximum quantity of the organic fluorine compounds. Most of the processes for removing the organic fluorine which have heretofore been utilized have been batch processes. Batch processes, as is readily understood, are ordinarily quite expensive.

I have now found that organic materials containing such organic fluorine-containing compounds can be treated by a continuous process in the presence of nonadsorptive carbon to effect decomposition of such organic fluorine compounds. The carbon, which has a surface area of between 0.01 and 5 square meters per gram, as determined by low temperature gas adsorption tests, acts as a true catalyst which promotes the decomposition of the organic fluorine cornpounds and makes possible concomitant recovery of a major portion of the hydrogen fluoride resulting from the decomposition of the organic fluorine compounds. The organic fluorine compounds are removed from the hydrocarbon materials and are converted to hydrogen fluoride and light hydrocarbon materials in a continuous process. The catalysis is promoted when a minor amount of hydronuoric acid is present during the dehydrofiuorination step. When hydrofluoric acid is utilized to promote the catalysis, between 0.1 and 1 weight per cent of hydrofluoric acid may be present in the distillation zone with the organic fluorine contaminated hydrocarbon material.

This invention is performed by packing a fractional distillation tower with nonadsorptive carbon aggregate and passing a feed stream containing organic fluorine compounds therethrough to effect a decomposition of the organic fluorine compounds to free hydrogen fluoride. The nonadsorptive carbon which I use has a surface area of between 0.01 and 5 square meters per gram, preferably between 0.2 and'l square meter per gram. Such carbon material is to be contrasted with commercially available activated adsorptive carbon which has a surface area of between 500 and 2000 square meters per gram. The hydrogen fluoride materials, together with low-boiling gaseous hydrocarbon materials, are removed from the upper portion of the fractional distillation chamber and the hydrogen fluoride is separated from the hydrocarbon materials.

My invention can be applied with particular advantage to the removal of fluorine compounds from efliuents of a hydrocarbon conversion process wherein hydrofluoric acid has been employed as a conversion catalyst, either alone or with a promoter such as boron trifluoride, or the like. In the practice of the process of my invention, hydrocarbon efiiuents of the conversion process, such as an alkylation of an isomerization process, are passed from a catalyst separator to fractional distillation means. in this forr the hydrocarbon efliuents Will have associated with them relatively minor amounts of hydrogen fluoride and of organic fluorine compounds. When such hydrocarbon effluents are in the liquid phase, as generally will be the case, these fluorine compounds will be present more or less completely therein as dissolved constituents, although 'an additional small amount of entrained hydrofluoric acid will sometimes be included. The fractional distillation means will remove, as a low-boiling product, a hydrogen fluoride fraction. Generally this fraction will also contain a lowboiling paraifln hydrocarbon, such as propane, a butane, or the like, in an amount at least sufficient to form with the hydrogen fluoride a lowboiling azeotropi'c mixture.

An object of this invention is to effect substantially complete removal of fluorine from hydrocarbon fluids containing organic fluorine compounds as impurities. Another object of the invention is to provide an improved continuous process for obtaining a substantially fluorinefree alk'ylate from the alkylation of hydrocarbons in the presence of a catalyst comprising a fluorine compound. Another object or the inyention is to remove organic fluorine compounds from other organic materials. Another object of the invention is to 'catalytically decompose organic fluorine compounds so as to release hydrogen fluoride. Another object of the invention is toeflect a simultaneous removal of hydrogen fluoride and organic fluorine compounds from low boiling hydrocarbon materials which contain such fluorine compounds as impurities. Other and further objects and advantages will be apparent, to those skilled in the art, upon study of the accompanying disclosure and discussion.

The drawing schematically portrays a flow plan and apparatus by which the process of this in- 'vention is readily carried out.

Referring now to the drawing, a suitable hydrocarbon material is charged to reactor chamber l1 through conduit l-2. Hydrofluoric acid is charged to the reactor as a catalyst for the reaction within reactor through conduit I3. As previously discussed, the invention can be applied to the effiuents of any one of a number of processes. Generally, however, the invention will be applied to paraflinic hydrocarbon eflluents of an alkylation process or of an isomerization process. When the process is one of alkylation, the hydrocarbon charge will comprise a mixture of paraflins and oleflns and the reaction conditions maintained in the reactor will be those well known to the art. When the process is one for isomerization of parafiin hydrocarbons, the hydrocarbon charge will comprise parafiins to be isomerized and the reaction conditions will be of separator l5 through conduit I6.

4 somewhat similar to those known for alkylation so far as temperature, pressure, and contact time are concerned. In either event, hydrogen fluoride may be the essential catalyst and if desired may be promoted by from about 1 to about 10 per cent by weight of boron trifluoride.

Efliuent material from reactor H is passed by means of conduit I4 into separator chamber IS. A hydrofluoric acid phase is formed in the lower portion of the separator chamber l5 and a hydrocarbon phase, generally in a liquid state and containing organic fluorine compounds is formed in the upper portion of the separator. Hydrofluoric acid is removed from the lower portion A portion of the hydrofluoric acid may be recycled to reactor H through conduit ll. Hydrocarbon material containing organic fluorine compounds is removed from the upper portion of separator [5 through conduit 18 and is passed into dehydrofluorinator It by way of conduits I8 and 20. Dehydrofluorin'ator I9 is packed with a nonadsorptive carbon aggregate material which may be in the form or Raschig rings or in the form of pellets of any other desirable shapes such as are used for packing in fractional distillation columns. Dehydrofluorinator I9 is maintained at distillation conditions of temperature and pressure. It is generally desirable to maintain the temperature within the dehydrofluorinator within the range of from F. to 300 F., the temperature being graduated from the bottom or ettle portion of the chamber to the upper or head portion of the chamber. Best operation is obtained when maintaining the kettle temperature of the dehydrofluorinator within the range of between 200 F. and 300 F. The organic fluorine material is decomposed in the presence of the nonadsorptive carbon catalyst and is removed from the upper portion of dehydrofluorinator I! in the form of hydrogen fluoride and gaseous low boiling hydrocarbon material.

Dehydrofluorinator I9 is operated in such a. manner that hydrogen fluoride and any boron trifluoride and the like, if such has been used, is removed by distillation as a low boiling fraction, generally accompanied by at least a suflicient amount of a low boiling paraflin hydrocarbon to form a low boiling azeotropic mixture therewith. This low boiling fraction is removed, generally as a gaseous mixture, through conduit 2| and at least a major portion of it is passed through cooler 22 in which the material is cooled and condensed. The condensed material can then be passed by means of conduit 23 to conduit l2 and reactor H, or through conduit 21 to conduit I4 and separator W. A minor portion of the gaseous mixture may be removed from conduit 2| by means of conduit 24 and passed to a point in the lower portion of dehydrofluorinator l9, preferably at or near the bottom of the dehydrofluorination zone which is associated With the distillation zone. This minor portion of gaseous mixture passes upwardly through the dehydro fluorination zone and promotes the reaction therein. In a preferred embodiment of the invention the material which is removed from separator I5 through conduit I8 is passed as aliquid to the upper portion of the fractional distillation zone as a combined feed and reflux stream, through conduits l8 and 20. Any material which is returned through conduit 24 to the lower portion of the dehydrofluorination zone is passed as a gaseous mixture to a :point well below the point of introduction of the combined feed and reflux stream. This material comprising free hydrogen fluoride is introduced in an amount such that a concentration of free hydrogen fluoride at the point of introduction is generally not thereto in the light of the teaching and discussion presented herein.

The following data are given to further illustrate and exemplify the invention. It will be in excess of l per cent by weight of free hydro- 5 understood that these data are exemplary only gen fluoride in the resulting mixture. and are not to be construed as limiting broader Although the invention has been described 1 embodiments of the invention. connection with the step of supplying free hy- Five routine tests were made relating to the drogen fluoride to the dehydrofluorination zone, invention disclosed in the discussion above. In conversion of the organic fluorine materials is four of the tests, free hydrogen fluoride was proalso accomplished quite economically without the vided in amounts within the range disclosed use of the free hydrogen fluoride. The activity hereinbefore, and in one of the tests carbon of the nonadsorptive carbon as the sole catalyst aggregate was utilized as the sole dehydrofluis such that a major portion of the organic fluoorination catalyst. In the first three tests, the rine material is continuously converted to hydro- 5 feed was supplied to a dehydrofluorinator which gen fluoride and low boiling gaseous hydrooarhad a column of 1% inches inner diameter bon material. and which column was packed with 4 inch car- Heat is supplied to dehydrofluorinator I9 by bon Raschig rings for a length of 8.75 feet, means of suitable heating equipment illustrated the carbon rings having a surface area of 0.5 by heating coil 25. Satisfactory operation is gensquare meter per gram. For the last two tests, erally obtained with a temperature at this point the inch carbon rings were removed from the of between 200 F. and 300 F. as disclosed above. column and a pipe having an outer diameter of Temperatures higher than the upper part of this 0.54 inch was placed in the column. The space range or lower than the low part of this range between the inserted pipe and the wall of the may be used in some instances. Excessive time column was packed for a length of 8.75 feet is ordinarily required to obtain satisfactory rewith inch carbon rings having the same surmoval of the organic fluorine, however, if lower face area per gram as the smaller rings. Contemperatures are used and excessively high presditions and results of the tests are set forth sures are encountered in connection with the disbelow in Table I. The feed which was utilized tillation if higher temperatures are used. If dein tests 1 and 2 s $911 forth below in Table II sired, or necessary, cooling and reflux at the top as feed 1. Feed 2 was utilized in test 3 and feed 3 of dehydrofluorinator l9 can be obtained by conwas utilized in tests 4 and 5. The organic fluventional equipment, illustrated by cooling coil 28. orine content of the feed used in each test is Best conversion is effected when dehydroflushown in Table I.

Table I 53 33 2% E1332? Org. F. wt, percent Frcc HF Wt., percent Percent Test Pressure, vol. of Dehydrop. s. 1. feed/vol. fiuonna- Head Kettle 5253 3 Feed Kettle Feed 9 55:; Kettle tion 187 233 235 1.7 0.155 0. 003 0.0021 0.27 87 0. 00s 99 190 234 234 1.7 0.024 0.011 0.0003 1.08 as 0. 003 09 190 234 230 1.8 0.145 0.184 0.035 0 0 as 194 234 205 2.3 0.137 0.120 0. 0238 0.44 00s as 104 234 205 2.2 0.0210 0. 0190 0.0042 0.07 54 0.003 27 orinator i0 is operated at an overall space velocity Table II (liquid volume of hydrocarbon/volume of cata- 5o lyst/hour) of between 1 and 3. Sufficient ap- Feed parent carbon surface is provided in dehydro- Constituents fiuorinator 19 to contact between 0.0001 and 0.1, 1 2 3 preferably between 0.003 and 0.03, barrel of feed for each apparent square foot of catalyst sur- 55 Propane as 8.4 8.4 face per hour. The overhead material from gg gg dehydrofluorinator l9, which is recycled to the Heavier n drocar'licii'fllilIIIIIIIIIIIIIIII 19:3 19:0 1010 reactor, generally constitutes between 20 weight p cent and 40 Weight per cent of the feed there The above data show the effectiveness of nonadsorptive carbon as the sole catalyst in the con- A high boiling liquid fraction which is free of version of t rganic fiuorjne ontajnin hydrogen fluoride and also substantially free of pounds The importance of a proper relationship Or an fluorine compounds is removed as a of surface area to flow is also indicated by the kettle product from the lower portion of dehyabove data. When the surface area of the catadrofluorinaitor 9 through conduit 25 and i5 lyst, which was available to the reaction, was passed to separating means, such as a fractionadecreased about twenty-five fold the organic tor, not shown. It will be obvious to those skilled fluorine content of the kettle product increased in the art that the drawing schematically illusabout twelve and fourteen fold for both high trates the use of conventional equipment which and low contents of organic fluorine in the feed. is not shown in detail and that considerable con- The results also indicate the value of promoting ventional equipment, such as heaters, coolers, the conversion by providing a minor amount of condensers, reflux equipment, pumps, compreshydrogen fluoride to the dehydrofluorination sors, catalyst chambers, and the like, will be zone. When for any reason the feed is free of necessary in the practice of any specific embodihydrogen fluoride, a small amount of hydrogen ment of the invention and can be readily adapted fluoride, such as 0.1 weight per cent or less to 1 weight per feed.

This invention has the advantage that practically no migration of the catalyst from the dehydrofluorinator is encountered. The problem of migration of silicon through the equipment from silicon containing catalysts is obviated hereby. Little or no reduction of catalyst by operation of the system is encountered with the nonadsorptive catalyst. The economic advantage obtained thereby is thus quite great.

Other and further modifications will be .apparent to those skilled in the art upon study of the accompanying disclosure and discussion. Such modifications are believed to be within the spirit and scope of the disclosure.

I claim:

1. In, a process of reducing the content of organic fluorine present as an impurity in a hydrocarbon material by subjecting the hydrocarbon material to distillation in contact with a solid dehydrofluorination, catalyst, the improvement which comprises using nonadsorptive carbomaggregate as: the sole -.dehydrofluorination. catalyst.

2 In process of reducing the content of organic fluorine present as an impurity in a hydrocarbon material by subjecting the hydrocarbon material to distillation in contact with a solid dehydrofluormation catalyst, the improvement which comprises using nonadsorptive carbonaggregate as a dehydrofluorination catalyst.

3. A process of, continuously reducing the content of organic fluorine present as an impurity in a hydrocarbon material which comprises the steps of passing said hydrocarbon material together with a minor amount of hydrofluoric acid through a nonadsolptive carbon-aggregate packed fractional distillation zone, said carbon having a surface area of between 0.01 and 5: square meters per gram; maintaining contents of said distillation zone under distillation. conditions of temperature and pressure; removing a low-boiling gaseous mixture comprising free hydrogen fluoride and a low-boiling paraffin hydrocarbon from said, distillation zone; and separating said cent ormore, may be added to the hydrogen fluoride and saidwlow-boiling parafiin hydrocarbon.

4. The process of claim3', wherein said minor amount of hydrofluoric acid comprises between 0.1 and 1 wei ht per cent; the contents of said distillation zone are maintained at a distillation temperature of not more than 300 F.; and passing said hydrocarbon material and hydrogen fluoride through said distillationzoneat a-n'over all space velocity of between 1 and 3., inclusive.

5. A process of continuously-reducing the'content of organic fluorine present as an impurity in a. hydrocarbon material without catalyst regeneration which comprises the steps of passing said hydrocarbon material through a nonadsorptive carbon-aggregate packed distillation zone at an overall space velocity of between 1 and 3, inclusive, said carbon having a surface area of between 0.01 and 5 square meters per gram; maintaining contents of said distillation zone at a distillation temperature of not more than 300 F.; converting said organic fluorine, in the presence of said carbon, to gaseous free hydrogen fluoride and gaseous low-boiling hydrocarbon; removing said hydrogen-fluoride and low-boiling hydrocarbon from said distillation zone; cooling and condensing a major portion of said gaseous mixture; and separating said hydrogen fluoride and said low-boiling hydrocarbon.

.6. The process of claim 5, wherein said carbon has a surface area of between 0.2 and 1 square meter per gram.

7. The process of claim 5, wherein between 0.1 and 1 weight per cent of hydrofluoric acid is added to said distillation zone with said organic fluorine contaminated hydrocarbon material.

8. In a process for the conversion of hydrocarbons in the presence of a fluorine-containing catalyst, the improvement which comprises passing el'liuents of such a hydrocarbon conversion to a settling zone; removing from said settling zone liquid hydrocarbon material containing a relatively small amount or organic fluorine compounds as impurities; passing said material together with between 0.1 and 1 weight per cent of hydrofluoric acid through a fractional distillation zone, said distillation zone being packed with nonadsorptive carbon in the form of Raschig rings, said carbon having a surface area of between 0.2 and 1 square meter per gram; maintaining contents within said distillation zone at a temperature within the range of between F. and 300 F.; converting said organic fluorine to hydrogen fluoride and gaseous low-boiling hydrocarbon in the presence of said carbon rings; removing said hydrogen fluoride and low-boiling hydrocarbons from said distillation zone and passing them to a separation zone; cooling and condensing said materials in said separation zone; separating said hydrogen fluoride and said lowboiling hydrocarbon; and removing from said distillation zone a high-boiling hydrocarbon fraction substantially free of hydrogen fluoride and organic fluorine compounds.

GERALD T. LEATHERMAN.

Name Date Grosse et al. Jan. 15, 1946 Number 

1. IN A PROCESS OF REDUCING THE CONTENT OF ORGANIC FLUORINE PRESENT AS AN IMPURITY IN AHY-YDROCARBON MATERIAL BY SUBJECTING THE HYDROCARBON MATERIAL TO DISTILLATION IN CONTACT WITH A SOLID DEHYDROFLUORINATION CATALYST, THE IMPROVEMENT WHICH COMPRISES USING NONADSORPTIVE CARBONAGGREGATE AS THE SOLE DEHYDROFLUORINATION CATALYST. 